<div>Self-assembled templates allow the creation of many complex arrays of nanostructures, which would be extremely difficult and expensive, if not impossible, to realize using any of the other available fabrication techniques. The complexity of these advanced nanostructures, synthesized using the various template assisted electrodeposition techniques, can be controlled to nanometer scale range by tuning the structural properties of the template, which is achieved by adjusting its various growth parameters during the self-assembly process.</div><div>Electrodeposition allows the creation of arrays of various metallic and semiconducting nanostructures. Monitoring the electrodeposition conditions permit the creation of single crystalline nanostructures of a particular material, or the formation of heterostructures using multiple electrodeposition steps. This work demonstrates the template assisted electrodeposition of vertically aligned nanowire arrays, both straight and branched, of metals, and a direct bandgap, III-V semiconductor, indium antimonide (InSb), which has one of the smallest known bandgap of any material. The template assisted electrodeposition of metallic, and InSb inverse opal (IO) structures is also shown, and the fabrication of a novel zipper shaped nanostructure by laser photomodification of a Ni IO structure is reported.</div><div>The optical characterization of the various nanostructures realized in this work have been examined. The results from this work confirm the ability to tune the optical spectra of nanostructures of the same material with similar volume fill fractions by structural modulation, where the different optical responses can be attributed to the structural differences of the actual structure as opposed to the material properties of the solid.</div>